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WO1990015098A1 - Agent de vulcanisation, procede de preparation et compose vulcanisable obtenu - Google Patents

Agent de vulcanisation, procede de preparation et compose vulcanisable obtenu Download PDF

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Publication number
WO1990015098A1
WO1990015098A1 PCT/JP1990/000686 JP9000686W WO9015098A1 WO 1990015098 A1 WO1990015098 A1 WO 1990015098A1 JP 9000686 W JP9000686 W JP 9000686W WO 9015098 A1 WO9015098 A1 WO 9015098A1
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WIPO (PCT)
Prior art keywords
group
curing agent
organic
component
positive integer
Prior art date
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Ceased
Application number
PCT/JP1990/000686
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English (en)
Japanese (ja)
Inventor
Takahisa Iwahara
Makoto Chiba
Tomoko Takahara
Kazuya Yonezawa
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Kanegafuchi Chemical Industry Co Ltd
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Kanegafuchi Chemical Industry Co Ltd
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Priority to EP90907475A priority Critical patent/EP0431173B1/fr
Priority to DE69021341T priority patent/DE69021341T2/de
Publication of WO1990015098A1 publication Critical patent/WO1990015098A1/fr
Anticipated expiration legal-status Critical
Priority to US08/313,923 priority patent/US5567833A/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • Curing agent method for producing the same, and curable composition using the same
  • the present invention relates to an organic cured product having a hydrosilyl group, a method for producing the same, and a curable composition using the curing agent.
  • the polyorganosiloxane described above generally has poor compatibility with organic polymers, and even if the polyorganohydrogensiloxane and the organic polymer containing an alkenyl group are cured, the polyorganosiloxane is phase-separated.
  • the hydrolysis and dehydrogenation / condensation reaction of Organo hydrodisiloxane was promoted, and there was a problem that sufficient mechanical properties could not be obtained due to voids.
  • the present invention solves these problems as a result of intensive studies in view of such circumstances, and is a curable liquid composition which is fast-curing and excellent in deep-curability, and is suitable for providing the composition. It is intended to provide an organic curing agent having a hydrosilyl group therein and a method for producing the same.
  • a non-polymer organic curing system containing at least two hydrosilyl groups in the molecule.
  • Good compatibility with alkenyl-containing organic polymer It is. Therefore, if the above components are cured using a hydrosilylation catalyst, the curable composition is uniform and has excellent mechanical properties such as rapid curing and deep curing, and the cured product has sufficient tensile properties.
  • an alkenyl group-containing organic base having all kinds of main skeletons can be used, it is possible to prepare a cured product applicable to a very wide range of uses.
  • the present inventors have found that an organic curing agent that is not a pedestal generally has a low viscosity and is advantageous in performing a work at the time of preparing a cured product.
  • a first gist of the present invention resides in an organic non-polymeric curing agent containing at least two hydrosilyl groups in a molecule.
  • a second gist of the present invention is to provide a catalyst for hydrosilation of an organic compound (A) containing at least one alkenyl group in a molecule and a polyhydric hydrodine silicone compound (B).
  • a compound containing at least one alkenyl group in a molecule
  • B polyhydric hydrodine silicone compound
  • the reaction is carried out so that the hydrosilyl group remains even after the reaction, and the non-polymeric organic curing agent containing at least two hydrosilyl groups in the molecule. Made It depends on the construction method.
  • a third aspect of the present invention is a curable composition
  • a curable composition comprising the following components (C), (D) and (E) as essential components;
  • Figure 1 shows the 300 MHz iH NMR spectrum of the bisphenol A diaryl ether obtained in Example 1;
  • FIG. 2 is a 300 MHz iH NMR spectrum of the Si—H group-containing ether-based curing agent obtained in Example 1,
  • Fig. 3 shows the ester curing agent containing Si-H group obtained in Example 5.
  • a non-polymeric organic compound having at least two hydrosilyl groups in the molecule which is the first invention of the present invention, is not particularly limited, and includes a group containing a hydrosilyl group.
  • R is a group selected from H, ⁇ 51 (01! 3 ) 3 and an organic group having 1 to 10 carbon atoms, and each R may be the same or different ( n is A positive integer and 2 ⁇ m ⁇ n ⁇ 50)
  • the hydrosilyl group is preferred because the organic curing agent containing the silyl group at the mouth of the present invention is less likely to impair the compatibility with various organic polymers.
  • the molecular weight of the group constituting the group is preferably 500 or less, and the following are also preferable in consideration of the reactivity of the hydrosilyl group.
  • H CH 3 identical molecules inhibit Doroshiri Le-containing groups in the there are two or more, they may be the same or different.
  • the total number of hydrosilyl groups contained in the organic curing agent containing no hydrosilyl group and which is not a pedestal may be at least two in one molecule, but is preferably 2 to 15 and is preferably 3 to 15. ⁇ 12 are particularly preferred.
  • the hydrosilyl group-containing organic curing agent of the present invention is mixed with various alkenyl group-containing organic bases in the presence of a hydrosilylation catalyst and cured by a hydrosilylation reaction, the hydrosilyl group is used. If the number is less than 2, the curing is slow and curing failure often occurs.c If the number of the silyl groups at the opening is more than 15, the stability of the curing agent deteriorates, and even after curing. A large amount of hydrosilyl groups remains in the cured product, causing void cracking.
  • the silyl group at the mouth is contained in the organic curing agent containing a silyl group at the mouth according to the present invention by the general formula (II)
  • X is a substituent containing at least one hydrosilyl group
  • R 2 is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more polyester bonds.
  • R 3 is an organic group having 1 to 30 carbon atoms, and a is an integer selected from 1 to 4.
  • R 2 is a divalent hydrocarbon group having 2 to 20 carbon atoms, the c specific to one or more ether bonds may be contained in the inside of the R 2 is —CH 2 CH 2 —, one CH 2 CH 2 CH 2 —, CH 3
  • R 3 is an aromatic or aliphatic mono- to tetravalent organic group having 1 to 30 carbon atoms. Specifically,
  • R 2 is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds.
  • R 4 An organic group having 1 to 30 carbon atoms, and a is an integer selected from 1 to 4.
  • R 4 is an aromatic or aliphatic monovalent to tetravalent organic group having 1 to 30 carbon atoms.
  • X is a group containing at least one hydrosilyl group
  • R 5 is a monovalent to tetravalent hydrocarbon group having 25.0 carbon atoms
  • a is an integer selected from 14).
  • pedestals There are various types of pedestals.
  • hydrosilyl group-containing organic curing agent of the present invention further include a compound represented by the general formula (I):
  • X is a group containing at least one hydrosilyl group
  • R 2 is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds.
  • R 6 is A monovalent to tetravalent organic group, and a is an integer selected from 1 to 4.).
  • R 2 is Formula ( ⁇ ), it is the same as R 2 in (IV ').
  • R 6 is CH 3- , CH 3 CH 2- , CH 3 CH 2 CH 2- ,
  • nCH 2 C'H (n is an integer of 1 to 5) CH 2 CH 2 CH 2 0) nCH 2 CH 2 CH 2- (n is an integer of 1 to 5)
  • n is an integer of 1 to 5).
  • the method for producing the hydrosilyl group-containing organic curing agent of the present invention there is no particular limitation on the method for producing the hydrosilyl group-containing organic curing agent of the present invention, and any method may be used.
  • a reducing agent such as LiAl2H ”NaBH to reduce the Si—C group in the compound to a Si—H group.
  • the second gist of the present invention relates to the above-mentioned (Hi) hydrosilyl group-containing organic system.
  • the present invention relates to a method for producing a curing agent. That is, an organic compound (A) containing at least one alkenyl group in the molecule and a polyhydric hydrosilicon compound (B) are reacted with a hydrosilyl group in the presence of a hydrosilylation catalyst.
  • the present invention relates to a method for producing a non-polymeric organic curing agent having at least two hydrosilyl groups in a molecule, characterized by reacting so as to remain.
  • component (A) various ether-based, ester-based, hydrocarbon-based, and carbonate-based compounds containing an alkenyl group can be used.
  • the ether compound used as the component (A) is not particularly limited, and may be any compound having an alkenyl ether group. Specifically, equation (W):
  • R 7 is a hydrocarbon group having 0 to 18 carbon atoms and may also contain one or more ether bonds.
  • R 8 is a hydrogen or methyl group
  • R 3 is a carbon group having 1 to 3 carbon atoms.
  • an organic group, a is an integer selected from 1 to 4, and a compound having an ether bond represented by the following formula: In the formula (VI),
  • R 7 represents a divalent hydrocarbon group having 0 to 18 carbon atoms, and R 7 may contain one or more ether linkages. Specifically — CH 2 ⁇ " ⁇ — H2 —, H2 CH2, CH 3
  • R 3 is an aromatic or aliphatic mono- to tetravalent organic group having 1 to 30 carbon atoms, and is the same as R 3 in the formula ( ⁇ ).
  • R 7 is a hydrocarbon group having 0 to 18 carbon atoms and may have one or more ether bonds. It may be contained.
  • R 8 is hydrogen or methyl group, R 4 is 1-3 carbon atoms
  • R 8 is hydrogen or a methyl group
  • R 5 is a mono- to tetra-valent hydrocarbon group having 2 to 50 carbon atoms
  • a is an integer selected from 1 to 4. Is mentioned.
  • R 5 is the same as R 5 in the formula (V).
  • R 7 is a hydrocarbon group having 0 to 18 carbon atoms and may contain one or more ether bonds.
  • R 8 is hydrogen or a methyl group, and Re is an organic group having 1 to 30 carbon atoms.
  • A is an integer selected from 1 to 4)
  • R 7 are as R 7 in formula (3 ⁇ 4), also R e is the same as R 6 in formula (I).
  • the polyvalent high Dorojiyu down Shi Li co emissions reduction stage thereof as the component (B) used in the present invention (CH 3) 2 SiH 2 , (CeH 5) 2 SiH 2, CH 3 SiH 3, C e H 5 SiH 3, (C 2 H 5) 2 SiH 2, CH 3 (CH 2) 5 mono Sila emission compound represented by SiH 3;
  • H (CH 3 ) 2 Si] 3 N, H (CH 3 ) 2 SiOC (CH 3 ) polysilicon compounds such as NSi (CH 3 ) 2 H;
  • the number of the silyl groups at the opening in one molecule of the polyhydric hydroxysilicon compound (B) is preferably from 2 to 16, particularly preferably from 3 to 13. .
  • Component (B) has a molecular weight of 500 or less, since it does not impair the solubility of the hydrosilyl group-containing organic curing agent of the present invention produced from component (B). I like it. Furthermore, in view of the high reactivity in the hydrosilylation reaction between the component (A) and the component (B) described later,
  • the hydrosilyl group-containing organic curing agent of the present invention comprises a component (A), an alkenyl group-containing organic compound, and a component (B), a polyhydric hydridion siliconized product.
  • the catalyst used in this process is a simple platinum support, solid platinum supported on a carrier such as alumina, silica, or carbon black.
  • catalysts other than platinum compounds include RhCl (P Ph 3 ) 3 , RhC 1 3, R h / A 1 2 03, RuC l 3, I rC 1 3, F eC l 3, A 1C 1 3, PdC 1 2 ⁇ 2 H 2 0, N iC l 2, T iC 1 4 etc. (P h represents a phenyl group). These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-one-year-old refin complex, platinum-bulsiloxane complex and the like are preferable.
  • catalytic amount is preferably used in the range of 1 0- 1 ⁇ 1 0- 8 mol relative to alkenyl groups in component (A). And it is preferably employed in the range of 1 0 ⁇ 1 0- 6 mol.
  • a solvent is not particularly required in the hydrosilylation reaction, but if the starting material is solid or of high viscosity and it is difficult to perform operations such as stirring, use an inert organic solvent as appropriate. This is not a problem.
  • examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane and octane; and ether-based solvents such as ethyl ether and butyl ether. And ketone solvents such as methylethylketone, and halogenated carbon such as trichloroethylene. Hydrogen solvents and the like are exemplified.
  • reaction temperature is 0 to 20 (TC, preferably 50 to 150. C. If the reaction temperature is lower than 0 ° C, the catalytic activity is not sufficient and the reaction rate is slowed down.
  • the hydrosilyl group-containing organic curing agent obtained by the above method usually contains a hydrosilylation catalyst even after the reaction, its stability is generally not good, so that it may be left for a long period of time, If the components are mixed in, the conversion of the 3-1 ⁇ group to Si-OH group occurs, and phenomena such as viscosity increase and gelation are observed. Therefore, it is desirable to remove the catalyst from the hydrosilyl group-containing organic curing agent after the hydrosilylation reaction.
  • the reaction solution is stirred with silica, silica gel, alumina, ion-exchange resin, etc., column-treated, or washed with a neutral or weakly acidic aqueous solution. Is exemplified.
  • the hydrosilyl group-containing organic curing agent obtained in this way generally has better compatibility with organic polymers than known hydrosilyl group-containing polysiloxanes. Therefore, if the organic curing agent containing a hydrosilyl group of the present invention and various organic polymers containing an alkenyl group are mixed and cured in the presence of the various hydrosilylation catalysts described above, The compatibility of the two components is good, so that the average —A cured product is obtained.
  • the curing conditions are not particularly limited, but curing is generally performed at 0 to 200 ° C, preferably at 50 to 150 ° C, for 10 seconds to 4 hours.
  • a cured product having a thickness of, for example, 1 or more is produced by the above-described method, a uniformly cured cured product having excellent deep curability can be obtained.
  • the properties of the cured product depend on the curing agent used and the molecular structure and molecular weight of the organic polymer, but can be produced from rubbery to resinous.
  • the hydrosilyl group-containing organic curing agent and the alkenyl group-containing organic polymer in addition to the three main components of the hydrosilylation catalyst, various solvents, if necessary, A plasticizer, a filler, a pot life extender, a pigment, an antioxidant, an ultraviolet absorber, an adhesion promoter, and the like may be optionally used.
  • a third gist of the present invention is a curable composition comprising the following components (C), (D) and (E) as essential components; (C) Non-polymeric organic curing agent containing at least two hydrosilyl groups in the molecule
  • Examples of the organic curing agent containing at least two hydrosilyl groups in the molecule, which is the component (C) of the present invention, include various ether-based, ester-based, hydrocarbon-based, and carbonate-based curing agents described in the first aspect. G-based curing agents can be used. The preferred molecular weight, molecular structure, structure of the silyl group of the opening and the number per molecule of the curing agent are the same as those described in the first gist of the present invention.
  • the method for producing the component (C) is not particularly limited, but is preferably produced by the method according to the second aspect of the present invention.
  • the organic polymer containing at least one alkenyl group in the molecule as the component (D) of the present invention is not particularly limited, and may have various main chain skeletons. One can be used.
  • polyester polymers such as polyoxyethylene-polypropylene-co-propylene copolymer, dibasic acids such as adipic acid, and glycol.
  • Acrylates such as latex and vinegar Vinyl acrylate, acrylonitrile, methyl methacrylate, acrylate copolymer with styrene, etc., graft polymer obtained by polymerizing vinyl monomer in the organic polymer, porsulfide Nylon 6 and hexamethylene diamine by ring-opening polymerization of ⁇ -aminoprolactam and nylon 66 and hexamethylene diamine by a degenerate platform of adipic acid Nylon 61 by condensation polymerization of sebacic acid Nylon 11 by s-amino undecanoic acid degenerate platform Nylon 12 by ring-opening polymerization of s-amino laurolactam 12, Nylon Among them, polyamide-based polymers having
  • the component (C) has good compatibility with the organic curing agent containing a hydrosilyl group
  • the body is preferred.
  • the combination of the two components (C) and (D) is a combination of an ether-based curing agent and a polyether-based polymer, an ester-based curing agent and a polyester-based polymer, and a hydrocarbon-based polymer and a hydrocarbon-based polymer. Particularly preferred is a combination.
  • the alkenyl group of the component (D) is not particularly limited, but may have the formula (XI):
  • An alkenyl group represented by is preferred.
  • Various methods can be used to introduce the alkenyl group into the organic polymer of the component (D).
  • the method of introducing the alkenyl group after the polymerization and the method of introducing the alkenyl group during the polymerization can be used.
  • an organic compound having a functional group such as a hydroxyl group or an alkoxide group at the terminal, main chain or side chain is used as a method of introducing an alkenyl group after the base.
  • An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having an active group and an alkenyl group having reactivity with the above functional group with the 4 ⁇ -polymer.
  • organic compounds having an active group and an alkenyl group that are reactive to the above functional groups include acrylic acid, methacrylic acid, butylacetic acid, acrylic acid chloride, and acrylyl.
  • Unsaturated fatty acid-substituted carbonate halides aryl chloride, aryl chloride, vinyl (methyl chloride) benzene, aryl (methyl chloride) benzene, aryl (bromomethyl) benzene, aryl (chloromethyl)
  • Examples include ether, aryl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, and aryloxy (chloromethyl) benzene.
  • an alkenyl group during polymerization for example, a radical
  • a vinyl monomer having a low radical reactivity alkenyl group in a molecule such as aryl methacrylate or aryl acrylate, or aryl mercapone is used.
  • a radical chain transfer agent having an alkenyl group having a low S-responsiveness an alkenyl group can be introduced into the main chain or at the terminal of the polymer.
  • the alkenyl group of the component (D) be present at the molecular terminal, since the effective network chain length of the cured product becomes longer.
  • the molecular weight of the component (D) is preferably from 500 to 50,000, particularly preferably from 500 to 2,000, in consideration of the properties of the cured product and the compatibility with the component (C).
  • the molar ratio of the hydrosilyl group to the alkenyl group is preferably from 0.2 to 5.0, and more preferably from 0.4 to 2.5. If the molar ratio is less than 0.2, the cured composition of the present invention can only provide a cured product with insufficient curing, stickiness and low strength, and a molar ratio of less than 5.0. As the size increases, a large amount of active silyl groups remain in the cured product even after curing, so that cracks and voids are generated, and a uniform and strong cured product tends not to be obtained.
  • hydrosilylation catalyst which is the component (E) of the present invention
  • any catalyst can be used.
  • the same catalyst as that used in the production of the hydrosilyl group-containing organic curing agent according to the second aspect of the present invention can be used.
  • These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum one-year-old olefin complex, platinum-vinylsiloxane complex and the like are preferable.
  • the amount of the catalyst is no particular limitation on the amount of the catalyst, but the amount of catalyst in component (D) is To the alkenyl group 1 mol 1 0 - 1 ⁇ not good to use in the range of 1 0- 8 mol.
  • 1 0 - is preferably used in the range of 3 ⁇ 1 0- s mol.
  • the curing conditions are not particularly limited, but are generally 0 to 200 ° C., preferably 30 to 150 ° C. It is good to cure at C for 10 seconds to 4 hours. In particular, at a high temperature of 80 to 150 ° C., a material which cures in a short time of about 10 seconds to 1 hour can be obtained.
  • the properties of the cured product depend on the molecular structure and molecular weight of the components (C) and (D) used, but can be produced from rubbery to resinous.
  • a solvent an adhesion improver, a physical property modifier, and a storage stability improver Agents, plasticizers, fillers, anti-aging agents, UV absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, amine-based radical chain inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments
  • Various additives such as foaming agents An agent can be appropriately added.
  • a polyoxypropylene having an aryl type olefin group at the terminal was prepared.
  • Polyoxypropylene glycol having an average molecular weight of 3000 and powdered sodium hydroxide were stirred at 60 ° C, and the reaction was performed by adding bromochloromethane to increase the molecular weight.
  • aryl chloride was added, and the terminal was aryl etherified at 110 ° C. This was treated with aluminum gayate to synthesize a purified terminally arylated polyoxypropylene.
  • the average molecular weight of this polyether was 960, and 92% of the terminal was a refined group (0.0231 mol / 10 Og) based on the iodine value.
  • the viscosity measured by an E-type viscometer was 130 boys (40 ° C.).
  • Equipped with stirring rod, dropping funnel, thermometer, three-way cock, cooling tube Prepare a oz-liH one-necked flask and prepare a polytetramethylene peroxide (trade name: Teratane-1) having an average molecular weight of about 2000 and a terminal silyl group at the end.
  • this polytetramethylene oxide has about 7
  • n-butyl acrylate 1 1 5.72 g, methyl methacrylate 60.0 Og, aryl methacrylate 2 ⁇ .16 g, n-dodecylmer force 6.46 g, azobisisobutyronitrile 2.0 g, toluene 400
  • a toluene solution of an acrylate monomer consisting of m was dropped into the flask in which toluene was refluxed over 5 hours from a dropping port under a nitrogen atmosphere. After the completion of the dropwise addition, the reaction was continued for 2 hours. The reaction solution was evaporated and further dried under reduced pressure at 80 for 3 hours to obtain about 195 g of a pale yellow viscous liquid oligoma.
  • the number of moles of aryl groups by iodine titration was 0.08 18 raol / 100 g, and the molecular weight by VP ⁇ was 2950, indicating that an average of 2.4 aryl groups were introduced per molecule.
  • the number average molecular weight was 3200 from the V ⁇ measurement of the obtained orange sesame.
  • the introduction of 1 ⁇ N MR Orefi down part of the scan Bae-vector than Ariru group of 300MHz came in the confirmation. Further, from the quantitative determination of the olefin by iodine titration, it was confirmed that an average of 1.83 aryl-type unsaturated groups (0.0573 mol / 100 g) were introduced in one molecule.
  • the hydrosilyl group-containing curing agent of Example 1 and the polymers of Synthesis Examples 2 to 5 were weighed so that the mole ratio of silyl group to aryl group was 1: 1.
  • a predetermined amount of the Si-H group-containing ether-based curing agent produced in Example 1, 9.54 g of various aryl group-containing polymers produced in Synthesis Examples 2 to 5, and platinum chloride used in Example 1 The acid catalyst solution was well stirred and mixed at the ratios shown in Table 2. The mixture was defoamed by centrifugation and poured into a polyethylene mold. After defoaming again at room temperature under reduced pressure, the mixture was cured at 100 for 1 hour to obtain a uniform rubbery cured product having a thickness of about 3 mm. A No. 3 dumbbell in accordance with JISK6301 was punched from the sheet of the cured product, and a tensile test was performed at a tensile speed of 20 Omnbinin. Table 3 shows the results. Table 3 shows that the use of the hydrosilyl group-containing ether-based curing agent of the present invention can be cured in a short time to produce a uniform rubber-like cured product.
  • dimethylsiloxane copolymer having an average molecular weight of about 2000 to 2100 PS 1.23 manufactured by Chisso Corporation
  • PS 1.23 manufactured by Chisso Corporation
  • the aryl group in each organic polymer and PS123 An attempt was made to produce a cured product in the same manner as in Example 3, except that the mol ratio of the drosyl group was 1.).
  • Each of the organic polymers containing an aryl group and the polysiloxane had poor compatibility and became turbid during mixing. Some were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and only a cured product with poor mechanical properties mixed with many bubbles could be obtained.
  • Example 4 The aryl-terminated polypropylene propylene oxide prepared in Synthesis Example 2 12.0 g, the silyl group-containing ether-based hardener obtained in Example 1 0.49 g (aryl group and hydrosilyl group)
  • the same chloroplatinic acid catalyst solution (14.3 / ⁇ ) as used in Example 1 and the molar ratio of groups was 1) was mixed well with stirring. After the mixture was defoamed by centrifugation, it was poured into a mold having a length of 6 cm, a width of 0.8 cm and a depth of 1.8 cra. After defoaming again at room temperature under reduced pressure, the mixture was cured at 100 ° C.
  • Organic polymers containing aryl groups Compatibility and curability with organic polymers.
  • Organic polymers containing aryl groups Organic polymers containing aryl groups.
  • Polymethylhydridodimethylsiloxane copolymer represented by The average molecular weight is about 2000 to 210, and a predetermined amount of PS123 (produced by Chisso Corporation) (the molar ratio of the aryl group in each organic polymer to the hydrosilyl group of PS123 is 1).
  • PS123 produced by Chisso Corporation
  • the organic polymer containing an aryl group and the polysiloxane had poor compatibility and became cloudy when mixed. Some were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and only a cured product with poor mechanical properties mixed with many bubbles was obtained.
  • the back surface was 19, and a sample with good deep curability was obtained.
  • chloroplatinic acid catalyst solution (11 2 Se (? ⁇ 6 Eta 2 0 lg of ethanol 1 g, 1, 2-dimethyl Tokisheta emissions 9 solution in g) of 20 id toluene 30
  • the melted material was charged into the dropper port.
  • the capsule was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 2 hours under an X 2 atmosphere.
  • the IR spectrum was measured. The absorption of the olefin around 164 Ocm- 1 had completely disappeared. To complete the reaction.
  • Predetermined amounts of the various aryl group-containing polymers produced in Mixture Examples 2 and 4 and the chloroplatinic acid catalyst solution used in Example 9 were mixed well at the ratios shown in Table 7.
  • the mixture was defoamed by centrifugation and poured into a polyethylene mold. After defoaming again under reduced pressure at room temperature, the mixture was cured at 100 ° C for 1 hour to obtain a uniform rubber-like cured product having a thickness of about 3 mm.
  • a No. 3 dumbbell compliant with JIS K6301 was punched out of the sheet of the cured product, and a tensile test was performed at a tensile speed of 20 Omnb min. Table 7 shows the results.
  • Table 7 shows that the composition using the hydrosilyl group-containing hydrocarbon-based curing agent of the present invention can be cured in a short time to produce a uniform rubber-like cured product. Power; Wakatsuta, Table 7
  • Example 2 Olygyl ether-terminated propylene oxide prepared in Example 2 100.Og Hydrocarbon hardener containing hydrosilyl group obtained in Example 9 0.3 Og (mol of arylyl and hydrosilyl groups) The same chloroplatinic acid catalyst solution 1 ° ⁇ 2 used in the ratio 1) and in Example 9 was mixed well with stirring. The mixture was poured into a polyethylene test tube having a diameter of about 1.5 cm and a length of about 10 cm, subjected to centrifugation and degassing under reduced pressure at room temperature, and then cured at 80 ° C for 1 hour. After curing, the bottom of the polyethylene test tube was cut and the cut surface was observed.
  • Example 13 A 200-inch four-necked flask was equipped with a cooling pipe with a three-way cock, a dropping funnel, a thermometer, a magnetic chip, and a glass stopper. Annular Porihai Dorojiyu down siloxane under N 2 atmosphere
  • the reaction mixture was evaporated to remove volatiles, yielding 10.2 g of a slightly viscous pale yellow transparent liquid.
  • the silyl group at the open mouth of the carbonate compound was confirmed as a strong absorption of 2170 cm- 1 in the IR spectrum.
  • the intensity ratio measured value 0.181
  • the curing agent was obtained.
  • the number of Si—H groups in the unit weight was calculated to be 0.47 mol / 100 g.
  • Table 8 shows the compatibility of the Si—H group-containing monolithic base material produced in Example 13 with the aryl group-containing organic polymer having various main chain skeletons.
  • a predetermined amount of the substrate and 1.Og of the organic substrate were mixed well, and after centrifugal defoaming, the mixed state was observed. Slightly; some with cloudiness; almost transparent and uniform.
  • the Si-H-containing compound has good solubility in various organic substrates That power.
  • a predetermined amount of a solution obtained by diluting the chloroplatinic acid catalyst solution used in Example 13 to 10 times was added to each of the above mixtures and mixed well.
  • Polymer with organic polymer 1 Polymer with: Polymer with: Polymer with: Polymer with: Polymer with: Polymer with: Polymer with:
  • a predetermined amount of dimethylsiloxane copolymer (average molecular weight of about 2000 to 2100, PS123 manufactured by Chitso Corporation) represented by the formula (aryl group in each organic polymer and PS123)
  • the organic polymer containing an aryl group and the polysiloxane had poor compatibility and became cloudy when mixed. Some of them were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and only a cured product with poor mechanical properties mixed with many bubbles could be obtained.
  • Example 16 10 g of arylether-terminated propylene oxide produced in Synthesis Example 2 and the hydroxysilyl group-containing carbonate obtained in Example 13 0.5 g (based on a molar ratio of aryl group and hydrosilyl group of 1) of the system compound and the same chloroplatinic acid catalyst solution 12 ⁇ used in Example 13 were well mixed with stirring.
  • the mixture was poured into a polyethylene test tube having a diameter of about 1.5 cm and a length of about 10 cm, subjected to centrifugation and degassing under reduced pressure at room temperature, and then cured at 80 ° C. for 1 hour. After curing, it was found that the cure uniformly when observing the cut surface by cutting the bottom of the port triethylene test tubes c

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

Composé vulcanisable contenant (1) un agent de vulcanisation organique non polymère comportant au moins deux groupes hydrosilyle dans sa molécule, (2) un polymère organique comprenant au moins un groupe alcényle dans sa molécule, et (3) un catalyseur d'hydrosilylation. On peut vulcaniser ce composé rapidement en profondeur de manière à obtenir un produit présentant de bonnes propriétés mécaniques.
PCT/JP1990/000686 1989-05-29 1990-05-29 Agent de vulcanisation, procede de preparation et compose vulcanisable obtenu Ceased WO1990015098A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP90907475A EP0431173B1 (fr) 1989-05-29 1990-05-29 Agent de vulcanisation, procede de preparation et compose vulcanisable obtenu
DE69021341T DE69021341T2 (de) 1989-05-29 1990-05-29 Härtungsmittel, verfahren zu seiner herstellung und damit hergestellte härtbare zusammensetzung.
US08/313,923 US5567833A (en) 1989-05-29 1994-09-26 Curing agent, preparation thereof and curable composition comprising the same

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JP13566889 1989-05-29
JP13566689 1989-05-29
JP13566789 1989-05-29
JP1/135666 1989-05-29
JP1/135668 1989-05-29
JP1/135667 1989-05-29
JP1/139940 1989-06-01
JP13994089 1989-06-01
JP1/145673 1989-06-07
JP1/145674 1989-06-07
JP14567489 1989-06-07
JP14567289 1989-06-07
JP1/145672 1989-06-07
JP14567389 1989-06-07
JP15314389 1989-06-15
JP1/153143 1989-06-15

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JP3002925B2 (ja) * 1992-04-08 2000-01-24 鐘淵化学工業株式会社 硬化性組成物
JP3287647B2 (ja) 1992-06-08 2002-06-04 鐘淵化学工業株式会社 太陽電池モジュール
DE4332425A1 (de) * 1993-09-23 1995-03-30 Wacker Chemie Gmbh Organopolysiloxane mit bifunktionellen endständigen Siloxaneinheiten
EP0709403A1 (fr) * 1994-10-28 1996-05-01 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition durcissable pour moulage par injection
JPH08253531A (ja) * 1995-01-17 1996-10-01 Kanegafuchi Chem Ind Co Ltd イソブチレン系重合体の製造方法及びイソブチレン系重合体
JPH08295783A (ja) * 1995-04-26 1996-11-12 Toray Dow Corning Silicone Co Ltd 硬化性樹脂組成物
DE19718470A1 (de) * 1997-04-30 1998-11-05 Wacker Chemie Gmbh Verfahren zur Herstellung von Si-gebundene Wasserstoffatome aufweisenden Organosiliciumverbindungen
WO1999024509A1 (fr) * 1997-11-06 1999-05-20 Kaneka Corporation Durcisseur, composition reticulable et composition de resine expansible contenant toutes deux ledit durcisseur, mousse fabriquee a partir de ladite composition de resine expansible et procede de fabrication correspondant
JP4993806B2 (ja) * 2000-04-21 2012-08-08 株式会社カネカ 光学材料用組成物、光学用材料、その製造方法およびそれを用いた液晶表示装置
EP1369458B1 (fr) 2000-12-27 2011-06-29 Kaneka Corporation Agents de durcissement, compositions durcissables, compositions pour materiaux optiques, materiaux optiques, leur production, afficheurs a cristaux liquides et diodes electroluminescentes ainsi obtenues
JP4833416B2 (ja) * 2001-01-17 2011-12-07 株式会社カネカ 硬化性組成物、製造方法、成形方法、および硬化物
FR2829141B1 (fr) * 2001-09-03 2006-12-15 Nexans Procede de fabrication d'un corps cylindrique et cable comportant un corps obtenu par ce procede
JP4610839B2 (ja) * 2002-03-08 2011-01-12 株式会社カネカ 封止剤、半導体等の封止方法、半導体装置の製造方法、および半導体装置
WO2003093349A1 (fr) * 2002-05-01 2003-11-13 Dow Corning Corporation Composes organohydrogenosilicium
WO2003093369A1 (fr) * 2002-05-01 2003-11-13 Dow Corning Corporation Compositions a duree de vie de bain amelioree
JP4802456B2 (ja) * 2004-06-02 2011-10-26 株式会社カネカ 硬化性組成物及び該硬化性組成物により封止された半導体装置
EP2163164B1 (fr) 2007-03-23 2016-01-27 Kaneka Corporation Mousse souple, procédé pour sa production, et absorbeur de chocs comprénant la mousse
US8273842B2 (en) 2007-11-09 2012-09-25 Kaneka Corporation Process for production of cyclic polyorganosiloxane, curing agent, curable composition, and cured product of the curable composition
KR101695493B1 (ko) * 2009-07-15 2017-01-11 엘지전자 주식회사 조리기기 및 제어방법
CN109942841B (zh) * 2019-03-27 2021-10-26 山东京博中聚新材料有限公司 一种丁基橡胶溶液及其制备方法

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US5548051A (en) * 1992-09-16 1996-08-20 E. I Du Pont De Nemours And Company Single component inorganic/organic network materials and precursors thereof

Also Published As

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EP0431173A1 (fr) 1991-06-12
JPH0395266A (ja) 1991-04-19
DE69021341T2 (de) 1996-02-15
EP0431173A4 (en) 1992-04-22
DE69021341D1 (de) 1995-09-07
EP0431173B1 (fr) 1995-08-02
JP2732315B2 (ja) 1998-03-30

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